The present invention relates to porphines, methods for making porphines, and the use of porphines in ink compositions.
U.S. patent application Ser. No. 08/757,222 filed Nov. 27, 1996, now U.S. Pat. No. 5,782,963; U.S. patent application Ser. No. 08/788,863 filed Jan. 23, 1997, pending; U.S. patent application Ser. No. 08/843,410 filed Apr. 15, 1997, now U.S. Pat. No. 5,855,655; U.S. patent application Ser. No. 08/903,911 filed Jul. 31, 1997, now U.S. Pat. No. 5,891,229; U.S. Provisional Patent Applications Serial Nos. 60/055,785 filed Aug. 15, 1997, and 60/062,643 filed Oct. 22, 1997; U.S. patent application Ser. No. 09/133,574 filed Aug. 13, 1998, pending; and U.S. patent application Ser. No. 09/058,385 filed Apr. 9, 1998, pending; all of which are assigned to Kimberly Clark Worldwide, Inc., disclose the use of a variety of porphines as colorant stabilizers. Porphines disclosed in the above-referenced applications include, but are not limited to, porphines having the following general structure: 
wherein R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO3H, 
COOH, or R1COOH wherein R1 is an alkyl group of from 1 to 6 carbons. R may also be in its corresponding salt form, such as SO3Na for SO3H or 
One such porphine is Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4) having the following structure: 
An attempt to make o-CuTPPS4 is disclosed in Treibs et al., Leibigs Ann. Chem., 718, 183, 1998 (hereinafter, xe2x80x9cTreibsxe2x80x9d). Treibs tried to prepare o-TPPS4 from 2-formylbenzenesulfonic acid, pyrrole, and propionoic acid. However, Treibs could not isolate the resulting product. Treibs reported a yield by GLC analysis of less than about 10%.
Although porphines provide excellent light stability to colorants, some porphines are relatively unstable and/or tend to xe2x80x9cyellowxe2x80x9d colorant compositions containing magenta dyes. A more desirable porphine molecule would be one that has at least one of the following characteristics: (1) the porphine molecule has less tendency to xe2x80x9cyellowxe2x80x9d a colorant composition, (2) the porphine molecule has the ability to make the colorant composition more xe2x80x9cbluexe2x80x9d; and (3) the porphine molecule, when used as a colorant, has superior lightfastness properties.
Further, while some of the above-described porphines provide excellent stability to one or more colorants associated with the porphines, they do not provide an orange/red color to a composition containing the porphines.
Accordingly, there exists a need in the art for a convenient, low cost, high yield method of making porphines, and compositions containing the porphines. Further, there exists a need for improved porphines, which are capable of providing superior colorant stability while being more stable themselves and without the tendency to xe2x80x9cyellowxe2x80x9d colorant compositions containing magenta dyes. Finally, there exists a need in the art for a new family of compounds that may be used alone as a colorant or may be used as a colorant stabilizer for one or more colorants associated with the new compounds.
The present invention addresses the needs described above by providing a new family of porphine compounds having the following general formula: 
where M is iron, cobalt or copper; R represents a halogenated alkyl group, 
wherein R1 to R77 each independently represent xe2x80x94H; a halogen; an alkyl group; a substituted alkyl group; an aryl group; a substituted aryl group; an alkoxy group; a nitrogen-containing group; a sulfur-containing group; xe2x80x94ORxe2x80x2, xe2x80x94NRxe2x80x2Rxe2x80x3, or xe2x80x94SRxe2x80x2, wherein Rxe2x80x2 and Rxe2x80x3 each independently represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.
The porphine compounds may be used as a magenta colorant and/or as a colorant stabilizer for other colorants. The new porphine compounds, when used as a colorant stabilizer, do not xe2x80x9cyellowxe2x80x9d magenta dyes. Consequently, unstable dyes, such as Acid Red 52, do not need to be used to make a magenta composition. The result is a more xe2x80x9cbluexe2x80x9d magenta color and a higher porphine to dye ratio, which creates superior light stability.
The present invention also addresses the needs described above by providing processes of making the above-described porphines at a lower cost and higher yields. The resulting porphines may be used as a colorant stabilizer for a variety of colorants, especially magenta colorants.
The present invention also relates to colorant compositions having improved stability and lightfastness, wherein the colorant is one or more of the new porphine compounds. The present invention also relates to the use of the porphine compounds in ink compositions and ink sets.
These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.
The present invention is directed to a new family of porphine compounds having the following general formula: 
where M is iron, cobalt or copper; R represents a halogenated alkyl group, 
wherein R1 to R77 each independently represent xe2x80x94H; a halogen; an alkyl group; a substituted alkyl group; an aryl group; a substituted aryl group; an alkoxy group; a nitrogen-containing group; a sulfur-containing group; xe2x80x94ORxe2x80x2, xe2x80x94NRxe2x80x2Rxe2x80x3, or xe2x80x94SRxe2x80x2, wherein Rxe2x80x2 and Rxe2x80x3 each independently represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Desirably, R1 to R77 each independently represent xe2x80x94H; a halogen; an alkyl group; a nitrogen-containing group; or a sulfur-containing group. More desirably, R1 to R77 each independently represent xe2x80x94H; chlorine; bromine; fluorine; iodine; a tert-butyl group; xe2x80x94NO2; xe2x80x94SO3H; xe2x80x94SO3Na; xe2x80x94SO3Cl; or xe2x80x94SO3Clxe2x88x92pyH+. Even more desirably, R1 to R77 each independently represent xe2x80x94H; chlorine; bromine; fluorine; or iodine. The new compounds may be used alone as an orange/red colorant or may be used as a colorant stabilizer.
The present invention also relates to colorant compositions having improved stability and lightfastness, wherein the colorant constitutes one or more of the above-described porphine compounds. Desirably, one or more of the new porphine compounds are admixed with a solvent system, as well as other composition components. The porphines may be used alone or in combination with at least one metal or metal salt. Suitable metals and metal salts are disclosed in U.S. Pat. No. 5,891,229, assigned to Kimberly Clark Worldwide, Inc., the entirety of which is incorporated herein by reference. As an example, the metal or metal salt in a composition can comprise a lanthanide or lanthanide salt. Moreover, a typical lanthanide or lanthanide salt comprises europium or europium salts. Optionally, the new porphine compounds may be associated with a molecular includant, chelating agent, or other material to improve solubility and/or interaction of the porphine compound and other colorants, if present. Suitable molecular includants, chelating agents, and other composition materials are also disclosed in U.S. Pat. No. 5,891,229. Typical molecular includants with which the porphines may be associated include one or more cyclodextrins, for example xcex1-cyclodextrin, xcex2-cyclodextrin, xcex3-cyclodextrin, xcex4-cyclodextrin, hydroxypropyl xcex2-cyclodextrin, or hydroxyethyl xcex2-cyclodextrin.
When used as a colorant stabilizer, the new porphine compounds may be associated with a variety of dyes or colorants. A suitable dye or colorant, for example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-xcex1-[4-(dimethylamino)phenyl]-xcex1-phenyl-benzene-methanol}, Malachite Green Carbinol hydrochloride {N-4-[[4-(dimethylamino)phenyl]phenyl-methylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)phenyl]phenylmethylium chloride}, and Malachite Green oxalate {N-4-[[4-(dimethylamino)-phenyl]-phenylmethylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)-phenyl]phenyl-methylium oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine monohydrochloride], Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and xcex2-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt]; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2-[(hydrazino-carbonyl)amino]-2,3-dihydro-1,3-dioxo-1H-benz[de]iso-quinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as Janus Green B {3-(diethylamino)-7-[[4-(dimethyl-amino)phenyl]azo]-5-phenylphenazinium chloride}; cyanine dyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz[e]indol-2-ylidene]-1,3,5-heptatrienyl]-1,1-dimethyl-3-(4-sulfobutyl)-1H-benz[e]indolium hydroxide inner salt sodium salt}; indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-3-one}; coumarin dyes, such as 7-hydroxy-4-methyl-coumarin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 [bisbenzimide or 2-(4-hydroxyphenyl)-5-(4-methyl-1-piperazinyl)-2,5-bi-1H-benzimidazole trihydro-chloride pentahydrate]; paraquinoidal dyes, such as Hematoxylin {Natural Black 1; 7,11b-dihydrobenz[b]-indeno[1,2-d]pyran-3,4,6a,9,10(6H)-pentol}; fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein); diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxy-benzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4-dinitro-phenyl)-1,4-phenylenediamine or Solvent Orange 53]; diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)naphthalene]; anthra-quinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone], and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo-1-naphthalenyl)-azo]-1-naphthalenyl)azo]-1,5-naphthalenedisulfonic acid tetrasodium salt}; xanthene dyes, such as 2,7-dichloro-fluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)-[29H,31H-phthalocyanato(2xe2x88x92)xe2x80x94N29,N30,N31,N32]copper}; carotenoid dyes, such as trans-xcex2-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-a-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-2-anthracene-carbonylic acid); azure dyes, such as Azure A [3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or 7-(dimethyl-amino)-3-imino-3H-phenothiazine hydrochloride]; and acridine dyes, such as Acridine Orange [Basic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridinium chloride mixture with 3,6-acridine-diamine).
The present invention is further directed to a convenient, fast, low cost, environmental-friendly process of making new porphine compounds. One process of making new porphine compounds proceeds by the following reaction, wherein N,N-dimethylformamide (DMF) is used as the solvent: 
Group Y Aldehydes: 
wherein R1 to R77 are as described above.
The above process produces TPPR4 (i.e., a porphine substituted with xe2x80x9cRxe2x80x9d groups) at yields of greater than 80%, and as high as about 96 to 97%. The TPPR4 is further reacted with a metal or metal salt, M, as defined above, to produce one of the porphine compounds of the present invention. The latter reaction proceeds at yields of greater than 90%, and as high as about 96 to 97%.
The reaction conditions for the above process may vary. Typically, the reaction may be carried out in a two-step process as follows. The reactants are purified by the following process or a similar purification process. The pyrrole is distilled under argon and a fraction is collected at 130xc2x0 C. The aldehyde reactant(s) is purified by a Dean and Stark method using benzene as the solvent. The solution is filtered at 60xc2x0 C. and the solid pumped in a vacuum oven overnight at room-temperature. The p-toluene sulfonic acid may also be purified by a Dean and Stark method using benzene as the solvent. It should be noted that a variety of one or more aldehyde reactants may be used in the above-described reaction.
In the first step, the aldehyde, N,N-dimethylformamide (DMF) and pyrrole are placed in a reaction vessel and stirred at room-temperature. The mixture is flushed with argon for about five minutes while stirring prior to heating. The mixture is then heated to 100xc2x0 C. for about ten to twelve minutes. The toluene sulfonic acid dissolved in 15 ml of DMF is injected into the reaction mixture. The reaction mixture is heated to 150xc2x0 C. and held at this temperature for about 50 minutes to form a porphine intermediate. DMF is removed under vacuum from the reaction mixture to yield a precipitate.
In the second step, the porphine intermediate is mixed with propionic acid. Air or oxygen is bubbled through the mixture at reflux for a period of time to yield a finished product. Conversion of the intermediate to the finished product may be monitored using an UV/VIS spectrometer. Reflux time may vary, but usually the reflux time is up to about 10 hours to convert the porphine intermediate to TPPR4. The TPPR4 is further reacted with a metal or metal salt, M, as defined above, to produce one of the porphine compounds of the present invention.
The choice of solvent in the first step of the above process may be any solvent, which enables the efficient production of TPPR4 and the new porphine compounds. Suitable solvents include, but are not limited to, DMF, dimethyl sulfoxide (DMSO), and dimethyl acetamide.
In one embodiment of the present invention, porphine compounds having superior lightfastness properties are produced having the following general formula: 
where M is iron, cobalt or copper; and R represents one or more substituents having at least one atom therein, wherein the at least one atom has a spin-orbit coupling constant greater than about 200 cmxe2x88x921. Suitable atoms having a spin-orbit coupling constant greater than about 200 cmxe2x88x921 include, but are not limited to, halogens. Desirably, the porphine compound contains at least one substituent having at least one atom therein, wherein the at least one atom has a spin-orbit coupling constant greater than about 500 cmxe2x88x921. More desirably, the porphine compound contains at least one substituent having at least one atom therein, wherein the at least one atom has a spin-orbit coupling constant greater than about 2400 cmxe2x88x921. Even more desirably, the porphine compound contains at least one substituent having at least one atom therein, wherein the at least one atom has a spin-orbit coupling constant greater than about 5000 cmxe2x88x921. In some porphine compounds, there may be a combination of two or more atoms wherein one atom has a spin-orbit coupling constant greater than about 500 cmxe2x88x921 and another atom has a spin-orbit coupling constant greater than about 5000 cmxe2x88x921. Any combination of such substituents is considered to be within the scope of the present invention.
It is believed that the above-described porphine compounds of the present invention possess superior lightfastness properties due to their reduced time in the excited state, as well as, their lower probability of being in the excited state. The presence of one or more R groups in the porphine having one or more substituents with high xe2x80x9cZxe2x80x9d values (i.e., atomic number) produces the so-called xe2x80x9cheavy atom effectxe2x80x9d that arises from the coupling of the spin angular momentum and orbital angular momentum. This so-called xe2x80x9cspin-orbit couplingxe2x80x9d, which generally increases with increasing Z values, enhances the rates of normally spin-forbidden electronic transitions, which enables the distribution of vibrational energy at an excited state, resulting from exposure to light, intramolecularly. The xe2x80x9cintramolecular quenchingxe2x80x9d of the molecule results in rapid quenching of the excited state back to the ground state. The net effect being a much smaller concentration of excited state species at any one time. A general discussion of xe2x80x9cheavy atom effectxe2x80x9d and xe2x80x9cspin orbital couplingxe2x80x9d, as well as values for spin orbit coupling constants, may be found in the Handbook of Photochemistry (Murov et al.), 2nd ed., pages 338-341, 1993, the entirety of which is incorporated herein by reference.
The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples, all parts are parts by weight unless stated otherwise.